Conversion of biomass into a liquid hydrocarbon material

ABSTRACT

A process for producing liquid hydrocarbon products from a biomass-containing feedstock and/or a biomass-derived feedstock is provided. The process comprises:
     a) contacting the feedstock with a hydropyrolysis catalyst composition and molecular hydrogen in a hydropyrolysis reactor vessel to produce a product stream comprising a partially deoxygenated hydrocarbon product, H 2 O, H 2 , CO 2 , CO, C 1 -C 3  gases, char and catalyst fines;   b) removing char and catalyst fines from said product stream;   c) cooling the remaining product stream to a temperature in the range of from 150 to 400° C.; and   d) hydroconverting said partially deoxygenated hydrocarbon product in a hydroconversion reactor in the presence of one or more catalyst compositions suitable for hydrodeoxygenation and aromatic saturation of the partially deoxygenated hydrocarbon product in the presence of H 2 O, CO 2 , CO, H 2 , and C 1 -C 3  gas generated in step a), to produce a vapour phase product comprising a C 4+  hydrocarbon product.

FIELD OF THE INVENTION

The invention relates to a process for converting a biomass-containingor biomass-derived feedstock into a liquid hydrocarbon material suitablefor use as a fuel or as a blending component in a fuel.

BACKGROUND OF THE INVENTION

With increasing demand for liquid transportation fuels, decreasingreserves of ‘easy oil’ (crude petroleum oil that can be accessed andrecovered easily) and increasing constraints on the carbon footprints ofsuch fuels, it is becoming increasingly important to develop routes toproduce liquid transportation fuels from alternative sources in anefficient manner.

Biomass offers a source of renewable carbon and refers to biologicalmaterial derived from living or deceased organisms and includeslignocellulosic materials (e.g., wood), aquatic materials (e.g., algae,aquatic plants, and seaweed) and animal by-products and wastes (e.g.,offal, fats, and sewage sludge). Liquid transportation fuels producedfrom biomass are sometimes referred to as biofuels. Therefore, whenusing such biofuels, it may be possible to achieve more sustainable CO₂emissions compared with petroleum-derived fuels.

However, in the conventional pyrolysis of biomass, typically fastpyrolysis carried out in an inert atmosphere, a dense, acidic, reactive,liquid bio-oil product is obtained. This product contains water, oilsand char formed during the process. The use of bio-oils produced viaconventional pyrolysis is, therefore, subject to several drawbacks.These include increased chemical reactivity, water miscibility, highoxygen content and low heating value of the product. Often theseproducts can be difficult to upgrade to fungible liquid hydrocarbonfuels.

An efficient method for processing biomass into high quality liquidfuels is described in WO2010117437, in the name of Gas TechnologyInstitute.

Solid feedstocks such as feedstocks containing waste plastics andfeedstocks containing lignocellulose (e.g. woody biomass, agriculturalresidues, forestry residues, residues from the wood products and pulp &paper industries and municipal solid waste containing lignocellulosicmaterial, waste plastics and/or food waste) are important feedstocks forbiomass to fuel processes due to their availability on a large scale.Lignocellulose comprises a mixture of lignin, cellulose andhemicelluloses in any proportion and usually also contains ash andmoisture.

The processes for the conversion of biomass into liquid hydrocarbonfuels described in WO2010117437 uses hydropyrolysis and hydroconversioncatalysts. While not being limited to any particular catalyst, exemplarycatalysts for use in such processes include sulfided catalystscontaining nickel, molybdenum, cobalt or mixtures thereof as activemetal(s). Other catalysts for use in the hydropyrolysis andhydroconversion steps for the conversion of biomass to liquidhydrocarbon fuels are described in co-pending applications IN4737/CHE/15, PCT/EP2015/064749, PCT/EP2015/064691 and PCT/EP2015/064732.

A process for producing liquid hydrocarbons from biomass that utilises ahydropyrolysis/hydroconversion process and a further downstreamhydroprocessing reactor containing reduced metal catalysts is describedin WO2015114008.

The products from any of these processes may be further separated toproduce diesel fuel, gasoline or blending components for gasoline anddiesel fuel.

Different specifications for gasoline and diesel fuel may be required indifferent locations. Material not meeting these specifications may beused as a blending component in a fuel or may need to be upgraded inorder to be used as a blending component or as the fuel itself.

Hydrocarbon liquid products produced from biomass byhydropyrolysis-based processes may not fulfil the specificationsrequired for diesel and gasoline range products in a number oflocations. For example, such material may have undesirable distributionof various classes of hydrocarbon molecules (aromatics, paraffins andnaphthenes) resulting in, for example, poor octane number of gasolineand poor cetane number of diesel product.

The art of hydropyrolysis, therefore, would benefit significantly fromprocesses that provide products with improvements in desired productquality attributes. The ability to produce fully fungible gasolineand/or diesel range products in a simple process from biomass is theultimate aim. A process with products that can be blended with existinggasoline and diesel fuels (i.e. those derived from crude oil) in highpercentages without affecting quality or performance would also behighly desirable.

SUMMARY OF THE INVENTION

Accordingly, the present invention provides a process for producingliquid hydrocarbon products from at least one of a biomass-containingfeedstock and a biomass-derived feedstock, said process comprising thesteps of:

a) contacting the biomass-containing feedstock and/or biomass-derivedfeedstock with a hydropyrolysis catalyst composition and molecularhydrogen in a hydropyrolysis reactor vessel at a temperature in therange of from 350 to 600° C., a pressure in the range of from 0.50 to7.50 MPa and a WHSV in the range of greater than 2.0 kg(biomass)/hour/kg (catalyst), to produce a product stream comprising apartially deoxygenated hydrocarbon product, H₂O, H₂, CO₂, CO, C₁-C₃gases, char and catalyst fines;b) removing all or a portion of said char and catalyst fines from saidproduct stream;c) cooling the remaining product stream to a temperature in the range offrom 150 to 400° C.; andd) hydroconverting all or a portion of said partially deoxygenatedhydrocarbon product in a hydroconversion reactor in the presence of oneor more catalyst compositions suitable for hydrodeoxygenation andaromatic saturation of the partially deoxygenated hydrocarbon product inthe presence of H₂O, CO₂, CO, H₂, and C₁-C₃ gas generated in step a), toproduce a vapour phase product comprising a C4+ hydrocarbon product,H₂O, CO, CO₂, and C₁-C₃ gases.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1 and 2 show representations of embodiments of prior artprocesses.

FIGS. 3 and 4 show non-limiting representations of embodiments of theprocess of the invention.

FIGS. 5 to 10 show the results of the examples described herein.

DETAILED DESCRIPTION OF THE INVENTION

The present inventors have found that an efficient and high yieldingprocess for the production of liquid hydrocarbon products can be carriedout by, in a first step, subjecting a biomass feedstock tohydropyrolysis in the presence of a hydropyrolysis catalyst. This stepis carried out at sufficiently high weight hourly space velocity (WHSV)of greater than 2.0 h⁻¹ such that the product hydrocarbons are onlypartially deoxygenated. After removal of solid by-products, the productstream is cooled to a temperature in the range of from 150 to 400° C.and then contacted with one or more catalyst compositions in ahydroconversion reactor. The one or more catalyst compositions allow forfurther deoxygenation and saturation of any aromatics present. Theresultant liquid hydrocarbon products have a low level of aromaticmaterials contained therein.

Biomass Feedstock

The feedstock used in the inventive process contains any combination ofbiomass-containing and/or biomass-derived feedstock.

The term ‘biomass’ refers to substances derived from organisms livingabove the earth's surface or within the earth's oceans, rivers, and/orlakes. Representative biomass can include any plant material, or mixtureof plant materials, such as a hardwood (e.g., whitewood), a softwood, ahardwood or softwood bark, lignin, algae, and/or lemna (sea weeds).Energy crops, or otherwise agricultural residues (e.g., loggingresidues) or other types of plant wastes or plant-derived wastes, mayalso be used as plant materials. Specific exemplary plant materialsinclude corn fiber, corn stover, castor bean stalks, sugar cane bagasse,sugar cane tops/trash, and sorghum, in addition to ‘on-purpose’ energycrops such as switchgrass, miscanthus, and algae. Short rotationforestry products, such as energy crops, include alder, ash, southernbeech, birch, eucalyptus, poplar, willow, paper mulberry, AustralianBlackwood, sycamore, and varieties of paulownia elongate. Other examplesof suitable biomass include organic oxygenated compounds, such ascarbohydrates (e.g., sugars), alcohols, and ketones, as well as organicwaste materials, such as waste paper, construction wastes, demolitionwastes, and biosludge.

Organic oxygenated compounds of particular interest include thosecontained in triglyceride-containing components, for example naturallyoccurring plant (e.g., vegetable) oils and animal fats, or mixtures ofsuch oils and fats (e.g., waste restaurant oils or grease).Triglyceride-containing components, which are representative ofparticular types of biomass, typically comprise both free fatty acidsand triglycerides, with the possible additional presence ofmonoglycerides and diglycerides. Triglyceride-containing components mayalso include those comprising derivative classes of compounds such asfatty acid alkyl esters (FAAE), which embrace fatty acid methyl esters(FAME) and fatty acid ethyl esters (FREE).

Examples of plant oils include rapeseed (including canola) oil, cornoil, colza oil, crambe oil, sunflower oil, soybean oil, hempseed oil,olive oil, linseed oil, mustard oil, palm oil, peanut oil, castor oil,coconut oil, jatropha oil, camelina oil, cottonseed oil, salicornia oil,pennycress oil, algal oil, and other nut oils, and mixtures thereof.Examples of animal fats include lard, offal, tallow, train oil, milkfat, fish oil, sewage sludge, and/or recycled fats of the food industry,including various waste streams such as yellow and brown greases.Mixtures of one or more of these animal fats and one or more of theseplant oils are also representative of particular types of biomass. Thetriglycerides and free fatty acids of a typical plant oil, animal fat,or mixture thereof, may include aliphatic hydrocarbon chains in theirstructures, with the majority of these chains having from about 8 toabout 24 carbon atoms. Representative plant oils and/or animal fats,used as a triglyceride-containing component, may include significantproportions (e.g., at least about 30%, or at least about 50%) ofaliphatic (e.g., paraffinic or olefinic) hydrocarbon chains with 16 and18 carbon atoms. Triglyceride-containing components may be liquid orsolid at room temperature. Representative triglyceride-containingcomponents, including plant oils and animal fats, either in their crudeform or pretreated, typically have a total oxygen content of about10-12% by weight. Solid granulated algae that is optionally dried to alow moisture content, may be a suitable type of biomass, and inparticular a triglyceride-containing component, in representativeembodiments.

Low-quality and/or crude triglyceride-containing components, such asbrown grease, are representative of biomass. Advantageously, suchtriglyceride-containing components may be introduced, according tospecific embodiments, directly into the hydropyrolysis reactor withoutpretreatment, such that the reactor itself effectively performs therequired transformations that allow the products of the hydropyrolysisof such low-quality and/or crude triglyceride-containing components, tobe further processed in a hydroconversion reactor in an effectivemanner. Representative triglyceride-containing components, for example,include those that have a total chloride or metals content, and in somecases a total alkali metal and alkaline earth metal content, of greaterthan about 10 ppm (e.g. from about 10 ppm to about 500 ppm), or greaterthan about 25 ppm (e.g. from about 25 ppm to about 250 ppm). Such levelsof contaminant chloride or metals, and particularly alkali and alkalineearth metals, are detrimental to catalyst activity in many types ofconventional hydroprocessing operations.

A biomass-containing feedstock may comprise all or substantially allbiomass, but may also contain non-biological materials (e.g., materialsderived from petroleum, such as plastics, or materials derived fromminerals extracted from the earth, such as metals and metal oxides,including glass). An example of a “biomass-containing” feedstock thatmay comprise one or more non-biological materials is municipal solidwaste (MSW).

Such municipal solid waste may comprise any combination oflignocellulosic material (yard trimmings, pressure-treated wood such asfence posts, plywood), discarded paper and cardboard, food waste,textile waste, along with refractories such as glass, metal. Prior touse in the process of this invention, municipal solid waste may beoptionally converted, after removal of at least a portion of anyrefractories, such as glass or metal, into pellet or briquette form.Co-processing of MSW with lignocellulosic waste is also envisaged.Certain food waste may be combined with sawdust or other material and,optionally, pelletised prior to use in the process of the invention.

Another specific example of a biomass-containing feedstock comprisesbiomass, as described herein, in addition to one or more oxygenatedpolymers (e.g., plastics) that contain oxygen in the functional groupsof their repeating monomeric substituents. The oxygen is at least partlyremoved in deoxygenation reactions occurring in the hydropyrolysisand/or hydroconversion reactors of processes described herein, throughthe production of H₂O, CO, and/or CO₂. The remainder of the polymericstructure may be used to generate either aliphatic or aromatichydrocarbons in the substantially fully deoxygenated hydrocarbon productor liquid hydrocarbon fuel. Representative oxygenated plastics have anoxygen content of at least 10% by weight (e.g., in the range from about10 to about 45% by weight), with specific examples of oxygenated plasticco-feeds being polycarbonates (e.g., (C₁₅H₁₆O₂)_(n), approx. 14% byweight O), poly (methyl methacrylate) (PMMA, (C₅H₈O₂)_(n), approx. 32%by weight O), polyethylene terephthalate (PET, (C₁₀H₈O₄)_(n), approx.33% by weight O), and polyamines (e.g. (CONH₂)_(n), approx. 36% byweight O). Due to the presence of hydrocarbon ring structures in certainoxygenated polymers (e.g. PET and polycarbonates), these oxygenatedpolymers may produce a relatively higher yield of aromatic hydrocarbonscompared to aliphatic hydrocarbons in processes described herein,whereas other oxygenated polymers may produce a relatively higher yieldof aliphatic hydrocarbons compared to aromatic hydrocarbons.

The term ‘biomass-derived’, for example when used in the phrasebiomass-derived feedstock, refers to products resulting or obtained fromthe thermal and/or chemical transformation of biomass, as defined above,or biomass-containing feedstocks. Representative biomass-derivedfeedstocks therefore include, but are not limited to, products ofpyrolysis (e.g. bio-oils), torrefaction (e.g. torrefied and optionallydensified wood), hydrothermal carbonisation (e.g. biomass that ispretreated and densified by acid hydrolysis in hot, compressed water),and polymerisation (e.g. organic polymers derived from plant monomers).Other specific examples of biomass-derived products (e.g. for use asfeedstocks) include black liquor, pure lignin, and lignin sulfonate.

Thermal and/or chemical transformation of biomass may occur in apretreatment step prior to, or upstream of, the use of the resultingbiomass-derived feedstock in processes described herein, including in ahydropyrolysis or hydroconversion step. Representative pretreating stepsmay use a pretreating reactor (pre-reactor), upstream of ahydropyrolysis reactor, and involve devolatilisation and/or at leastsome hydropyrolysis of a biomass-containing feedstock. Suchdevolatilisation and optional hydropyrolysis may be accompanied byother, beneficial transformations, for example to reduce corrosivespecies content, reduce hydropyrolysis catalyst poison content (e.g.reduce sodium), and/or a reduce hydroconversion catalyst poison content.Pretreatment in a pre-reactor may be carried out in the presence of asuitable solid bed material, for example a pretreating catalyst, asorbent, a heat transfer medium, and mixtures thereof, to aid ineffecting such supplemental transformations and thereby improve thequality of the biomass-derived feedstock. Suitable solid bed materialsinclude those having dual or multiple functions. In the case of apretreating catalyst, those having activity for hydroprocessing of thebiomass, described herein, are representative. Certain pretreatedfeedstocks, for example resulting or obtained from devolatilisationand/or at least some hydropyrolysis, are also biomass-derivedfeedstocks, whereas other pretreated feedstocks, for example resultingor obtained from classification without thermal or chemicaltransformation, are biomass-containing feedstocks, but notbiomass-derived feedstocks.

Biomass-derived feedstocks also include products of a Biomass to Liquid(BTL) pathway, which may be products of Fischer-Tropsch (F-T) synthesis,and more specifically the products of gasification, followed by F-Tsynthesis. These products are generally of significantly lower quality,compared to their counterpart, paraffin-rich petroleum derived productsused for fuel blending. This quality deficit results from the presenceof biomass-derived aliphatic alcohols and other biomass-derived organicoxygenated by-product compounds, as well as possibly reactive olefins,with amounts of these non-paraffinic impurities depending on the F-Tcatalyst system and processing conditions used. Representative totaloxygen contents of F-T synthesis products, as biomass-derivedfeedstocks, are typically in the range from about 0.25% to about 10%,and often from about 0.5% to about 5% by weight. In addition, productsof F-T synthesis, including F-T waxes, have a wide carbon number (andconsequently molecular weight) distribution and very poor cold flowproperties. Both of these characteristics may be improved usingappropriate transformations in processes described herein, for examplein the hydroconversion step, to convert F-T waxes into a paraffin-richcomponent, with a lower average molecular weight (and narrower molecularweight distribution) and/or with a greater degree of branching (orcontent of isoparaffins), in order to meet specifications for distillatefuel fractions of the substantially fully deoxygenated hydrocarbonproduct or liquid hydrocarbon, such as a diesel boiling range fractionand/or an aviation (e.g., jet) fuel boiling range fraction.

Gasification (e.g., non-catalytic partial oxidation) of a wide varietyof carbonaceous feedstocks, including biomass as defined above, mayprovide the syngas used for F-T synthesis. F-T synthesis refers to aprocess for converting syngas, namely a mixture of CO and H₂, intohydrocarbons of advancing molecular weight according to the reaction:

n(CO+2H₂)→(—CH₂—)_(n) +nH₂O+heat.

The F-T synthesis reaction generates reaction products having a widerange of molecular weights, from that of methane to those of heavyparaffin waxes. The particular mixture of generally non-cyclicparaffinic and olefinic hydrocarbons, as well as the proportions ofthese reaction products, are governed substantially by the catalystsystem used. Normally, the production of methane is minimised and asubstantial portion of the hydrocarbons produced have a carbon chainlength of a least 5 carbon atoms. Therefore, C₅ ⁺ hydrocarbons arepresent in the F-T synthesis product in an amount generally of at leastabout 60% (e.g., from about 60% to about 99%), and typically at leastabout 70% (e.g. from about 70% to about 95%) by weight. The F-Tsynthesis product may be pretreated for the removal of lighthydrocarbons (e.g., C₁-C₄ hydrocarbons) and water. However, since thesecomponents are well-tolerated in processes described herein, and areeven beneficial in some cases (e.g., for the production of requiredhydrogen via reforming), raw products of F-T synthesis (i.e., withoutpretreatment) may also be suitable as biomass-derived feedstocks. Suchraw products may have a combined, C₁-C₄ hydrocarbon and oxygenatedhydrocarbon content of greater than about 1% by volume, and even greaterthan 5% by volume.

As in the case of certain F-T synthesis products, other types of crudeor low-quality biomass or biomass-derived feedstocks, for exampleparticular triglyceride-containing components such as brown grease, maybe pretreated. Brown grease includes solid particulates such as rottenfood particles. Crude triglyceride-containing components may otherwiseinclude phospholipids (gums) and metal contaminants, including alkaliand alkaline earth metals. Due to a high solids content, highhydroconversion catalyst poison content, and/or propensity to causehydroconversion catalyst plugging, low-quality and/or crudetriglyceride-containing components may be suitably upgraded bypretreatment to reduce the content of solids or other of theseundesirable materials. A pretreated triglyceride-containing componentrepresents a particular type of biomass-derived feedstock.

Biomass-derived feedstocks also extend to pretreated feedstocks thatresult or are obtained from thermal and/or chemical transformation,prior to, or upstream of, their use as feedstocks for processesdescribed herein. Particular biomass-derived feedstocks are conventionalpyrolysis oils, i.e. products of conventional pyrolysis processes,including fast pyrolysis processes as described in U.S. Pat. No.5,961,786, CA1283880 and by Bridgwater, A. V., ‘Biomass Fast Pyrolysis’Review paper BIBLID: 0354-9836, 8 (2004), 2, 21-49). Representativebiomass-derived feedstocks in which the original lignocellulosiccomponents have been transformed may comprise a significant quantity,for example generally from about 5% to about 85%, and often from about10% to about 75%, by weight of cyclic compounds, including cyclicorganic oxygenates. The term “cyclic organic oxygenates” is meant toinclude compounds in which oxygen is incorporated into a ring structure(e.g., a pyran ring), as well as compounds (e.g., phenol) having a ringstructure with oxygen being incorporated outside the ring structure. Ineither case, the ring structure may have from 3 to 8 ring members, befused to other ring structures, and may be completely saturated (e.g.,naphthenic), completely unsaturated (e.g., aromatic), or partiallyunsaturated. After being subjected to hydroconversion in processesdescribed herein, these cyclic compounds, including cyclic organicoxygenates, may contribute to the total aromatic hydrocarbon content ofthe substantially fully deoxygenated hydrocarbon product or liquidhydrocarbon fuel. These cyclic compounds are preferably obtained fromnatural sources, such as lignocellulosic biomass, as described above,that has been pyrolyzed to depolymerise and fragment the cyclic buildingblocks of cellulose, hemicellulose, and lignin.

A representative biomass-derived feedstock is therefore conventionalpyrolysis oil (bio-oil), containing significant quantities of cycliccompounds (e.g., generally from about 10% to about 90% by weight, andtypically from about 20% to about 80% by weight), as described above,that are precursors, in processes described herein, to aromatichydrocarbons. Pyrolysis oil contains often from about 30% to about 40%,by weight of total oxygen, for example in the form of both (i) organicoxygenates, such as hydroxyaldehydes, hydroxyketones, sugars, carboxylicacids, and phenolic oligomers, and (ii) dissolved water. For thisreason, although a pourable and transportable liquid fuel, pyrolysis oil(and particularly raw pyrolysis oil that has not been pretreated) hasonly about 55-60% of the energy content of crude oil-based fuel oils.

Representative values of the energy content are in the range from about19.0 MJ/liter (69,800 BTU/gal) to about 25.0 MJ/liter (91,800 BTU/gal).Moreover, this raw product is often corrosive and exhibits chemicalinstability due to the presence of highly unsaturated compounds such asolefins (including diolefins) and alkenylaromatics. In processes asdescribed herein, pyrolysis oil may be further deoxygenated and undergoother transformations to yield hydrocarbons in the substantially fullydeoxygenated hydrocarbon liquid or liquid hydrocarbon fuel recoveredfrom the hydroconversion step. According to some embodiments, aromatichydrocarbons derived from conventional pyrolysis oil may be concentratedin a liquid product following fractionation of the substantially fullydeoxygenated hydrocarbon liquid, whereby the product is suitable forblending in fuels, such as gasoline, or otherwise is useful as such afuel without blending (e.g., a gasoline boiling range fraction meetingone or more, and possibly all, applicable gasoline specifications).

Further specific examples of biomass-derived feedstocks includeby-products of Kraft or sulfate processing for the conversion of woodinto pulp. These by-products include black liquor, tall oil, purelignin, and lignin sulfonate. Tall oil refers to a resinous yellow-blackoily liquid, which is namely an acidified by-product of pine woodprocessing. Tall oil, prior to refining, is normally a mixture of rosinacids, fatty acids, sterols, high-molecular weight alcohols, and otheralkyl chain materials. Distillation of crude tall oil may be used torecover a tall oil fraction (depitched tall oil) that is enriched in therosin acids, for use as a biomass-derived feedstock that produces arelatively higher yield of aromatic hydrocarbons compared to aliphatichydrocarbons.

Naturally derived (e.g., non-fossil derived) oils rich in cycliccompounds, and therefore useful as biomass-derived feedstocks, includingpyrolysis oil, and Kraft or sulfate processing by-products (e.g., blackliquor, crude tall oil, and depitched tall oil) as described herein,have a high oxygenate content that is detrimental to their value for useas biofuels, without deoxygenation. In the case of tall oil, forexample, rosin acids (all multi-ring organic acids) are present insignificant concentrations. Deoxygenation of these oxygenated cycliccompounds under hydropyrolysis and/or hydroconversion conditionsbeneficially yields aromatic hydrocarbons. In combination with oxygenremoval, ring saturation and/or ring opening of at least one ring (butnot all rings) of the multi-ring compounds leads to the formation ofnaphthenic and/or alkylated cyclic hydrocarbons, respectively.Importantly, the naphthenic/aromatic hydrocarbon equilibrium under theparticular hydropyrolysis and/or hydroconversion conditions used, may beused to govern the relative proportions of these species and therebymeet desired specifications for a particular application, for examplethe yield, or content, of aromatic hydrocarbons in a gasoline boilingrange fraction or aviation fuel boiling range fraction of thesubstantially fully deoxygenated hydrocarbon product or liquidhydrocarbon, as needed to meet desired specifications (e.g. octanenumber in the case of gasoline specifications or aromatic hydrocarboncontent in the case of aviation (non-turbine or jet) fuelspecifications).

Yet further examples of biomass-derived feedstocks include oils obtainedfrom aromatic foliage such as eucalyptols, as well as solid granulatedlignin that is optionally dried to a low moisture content. Theseexamples can also ultimately lead to the formation of aromatichydrocarbons in the substantially fully deoxygenated hydrocarbon productor liquid hydrocarbon fuel.

Representative biomass-derived feedstocks may be pretreated to improvequality, prior to introduction into processes as described herein. Talloil, for example, may be used either in its crude form or may otherwisebe pretreated by distillation (e.g., vacuum distillation) to removepitch (i.e., providing depitched tall oil) and/or concentrate the rosinacids, which are primarily abietic acid and dehydroabietic acid butinclude other cyclic carboxylic acids. A biomass-derived feedstock mayin general be obtained by a pretreatment involving separation to removeunwanted materials, for example from a crude tall oil or a crudepyrolysis oil (bio-oil). In the case of crude bio-oil, for example,pretreatment by filtration and/or ion exchange may be used to removesolids and/or soluble metals, prior to introduction of the pretreatedbio-oil to a process as described herein. According to otherembodiments, biomass-derived feedstocks in a crude or low-quality form,such as crude bio-oil or black liquor, may also be advantageouslyintroduced directly into processes as described herein without suchpretreatment steps, such that one or more process steps (e.g.,hydropyrolysis and/or hydroconversion) may itself perform the necessarypretreatment and/or desired further transformations to ultimately yieldliquid hydrocarbons. In the case of a hydropyrolysis reactor performinga pretreatment step, the deoxygenated hydrocarbon product, includingproducts of the hydropyrolysis of a crude or low-quality biomass-derivedfeedstock, can be further processed in a hydroconversion step in aneffective manner.

Any of the types of biomass-containing and biomass-derived feedstocksdescribed herein may be combined and introduced to processes asdescribed herein, or otherwise introduced separately, for example atdiffering axial positions into the hydropyrolysis and/or hydroconversionreactor. Different types of biomass-containing and/or biomass-derivedfeedstocks may be introduced into either the hydropyrolysis reactor orthe hydroconversion reactor, although, according to particularembodiments described above, the introduction into one of these reactors(e.g., in the case of a crude or low-quality biomass-derived feedstockbeing introduced into the hydropyrolysis reactor vessel) may bepreferable.

Hydropyrolysis Step

The hydropyrolysis catalyst composition of the present inventionpreferably comprises one or more active metals selected from cobalt,molybdenum, nickel, tungsten, ruthenium, platinum, palladium, iridiumand iron. Preferably, the one or more active metals are selected fromcobalt, molybdenum, nickel and tungsten.

The metals present in the hydropyrolysis catalyst composition used inthe process of the present invention are supported, preferably on ametal oxide support. Metal oxides useful as supports for thehydropyrolysis catalyst composition include alumina, silica, titania,ceria, zirconia, as well as binary oxides such as silica-alumina,silica-titania and ceria-zirconia. Preferred supports include alumina,silica and titania. The most preferred support is alumina. The supportmay optionally contain recycled, regenerated and revitalised fines ofspent hydrotreating catalysts (e.g. fines of CoMo on oxidic supports,NiMo on oxidic supports and fines of hydrocracking catalysts containingNiW on a mixture of oxidic carriers and zeolites).

Total metal loadings on the hydropyrolysis catalyst compositions arepreferably in the range of from 0.05 wt % to 3 wt % for noble metals(e.g. ruthenium, platinum, palladium and iridium) and from 1 wt % to 75wt % for base metals (e.g. cobalt, molybdenum, nickel, tungsten andiron) (weight percentages are expressed as a weight percentage of totalof all active metals on the calcined catalyst in their reduced(metallic) form).

Additional elements such as one or more of phosphorous, boron and nickelmay be incorporated into the catalyst to improve the dispersion of theactive metal.

The hydropyrolysis catalyst composition used in the process of thepresent invention may be prepared by any suitable method known in theart. Suitable methods include, but are not limited to co-precipitationof the active metals and the support from a solution; homogeneousdeposition precipitation of the active metals on the support; porevolume impregnation of the support with a solution of the active metals;sequential and multiple pore volume impregnations of the support by asolution of the active metals, with a drying or calcination step carriedout between successive pore volume impregnations; co-mulling of thesupport with a solution or a powder containing the active metals.Further, a combination of two or more of these methods may also be used.

The hydropyrolysis catalyst composition may be provided to the reactorin either an oxidic state, in a sulfided or sulfurised state or in apre-reduced state. Preferably, the hydropyrolysis catalyst compositionis provided in a oxidic or a pre-reduced state, more preferably in anoxidic state to the reactor in the process of the present invention.

Therefore, in one embodiment of the invention, after preparation by oneof the above or another method, the compositions thus-formed aresuitably calcined in the presence of air or oxygen in order to obtainthe oxidic state. By the term ‘oxidic state’ as used herein is meantthat 95% or more of the active metal atoms present are present in anoxidation state greater than zero as oxides. For example, a supportedoxidic cobalt catalyst has more than 95% of the cobalt present in the +2or +3 oxidation state, as oxides, and a supported oxidic nickel catalysthas more than 95% of the nickel present in the +2 oxidation state, asoxide.

In another embodiment of the invention, after preparation by one of theabove or another method, the compositions thus-formed are suitablysubjected to a reduction step in order to convert at least a portion ofthe active metals into their fully reduced state. This can be carriedout by subjecting the catalyst to a reducing gas (for example, gascontaining hydrogen) at elevated temperatures and elevated pressures.The temperatures of the reduction step can vary from 120° C. to 450° C.and pressures can vary from 0.1 megapascal to 10 megapascal.

In a further embodiment of the invention, after preparation by one ofthe above or another method, the compositions thus-formed are suitablysubjected to a sulfidation step in order to convert at least a portionof the active metals into their sulfided form. This can be carried outby subjecting the catalyst to a sulfur-containing fluid at elevatedtemperatures and pressures. Typical sulfur containing fluids includeliquid hydrocarbons containing sulfur dopants or sulfur compoundsoccurring naturally in the hydrocarbons, and gaseous streams containinghydrogen sulfide. In this embodiment of the invention, the one or moreactive metals are preferably selected from cobalt, molybdenum, nickel,iron and tungsten. Typical pressures for sulfidation step range from 0.5MPa to 10 MPa, while typical temperatures range from 150° C. to 450° C.Alternatively, the catalysts may be sulfurised, such that sulfur speciesare present on the catalyst, which sulfur species will react with theactive metal under the conditions in the reactor vessel in order to fromthe sulfided catalyst.

It will be readily apparent that, although the hydropyrolysis catalystcomposition provided in the hydropyrolysis reactor will initiallycomprise metal or metals in their oxidic, sulfided or reduced states,the chemical form of the catalyst composition will undergo a changeunder the operating environment of the process, resulting in a change inthe chemical form of the active metals on the catalyst and of thesupport as well. This change will involve phenomena resulting from theinteraction of the catalyst with the reactant gas (hydrogen, carbonmonoxide, carbon dioxide), products (hydrocarbons) and by-products(water, carbon monoxide, carbon dioxide, ammonia, hydrogen sulfide etcetera) under the temperature and pressure conditions of the process.

It is postulated, without wishing to be bound by theory, that theinitial chemical composition will be transformed under the conditions ofthe process of the invention into a composition where a portion of theactive metals may be in reduced form (with an oxidation number of zero),another portion of the active metals may be in a higher oxidation statein sulfided form (forming a chemical bond with sulfur atoms present inthe biomass feedstock) and yet another portion of the active metals maybe in a higher oxidation state in oxidic form (with oxygen atomsavailable from the biomass feedstock or from the catalyst itself).

Further catalyst may be added to the process as it progresses in orderto replace catalyst lost through attrition. Such catalyst will also beinitially provided to the reactor with the active metals being presentin their oxidic, sulfided or pre-reduced state, depending on the stateof the original catalyst composition.

The hydropyrolysis catalyst composition is preferably present in theform of spherical catalyst particles. Catalyst particles sizes, for usein a commercial reactor in the hydropyrolysis step, are preferably inthe range of from 0.3 mm to 4.0 mm, more preferably in the range of from0.6 mm to 3.0 mm, and most preferably in the range of from 1 mm to 2.4mm.

Although any type of reactor suitable for hydropyrolysis may beemployed, the preferred type of reactor is a bubbling fluidised bedreactor. The fluidisation velocity, catalyst size and bulk density andfeedstock size and bulk density are chosen such that the catalystremains in the bubbling fluidised bed, while the char produced getsentrained out of the reactor.

The hydropyrolysis is suitably carried out in the hydropyrolysis reactorvessel at a temperature in the range of from 350° C. to 600° C. and apressure in the range of from 0.50 MPa to 7.50 MPa. The heating rate ofthe biomass is preferably greater than about 100 W/m². The weight hourlyspace velocity (WHSV) in g (biomass)/g (catalyst)/hr for this step isgreater than 2.0 h⁻¹. Preferably, the WHSV in the hydropyrolysis reactorvessel is no more than 6 h⁻¹ more preferably no more than 5 h⁻¹.

Such a high WHSV limits the amount of hydrodeoxygenation achieved by thehydropyrolysis catalyst. It will be readily understood that the WHSVshould be limited to prevent the product stream from the hydropyrolysisreactor having undergone too little devolatilisation or too littlehydrodeoxygenation, thus, being too reactive.

Char Removal, Cooling and Other Process Steps

Char and catalyst fines are removed from the product stream of thehydropyrolysis step. Any ash present will normally also be removed atthis stage. The most preferred method of char and catalyst fines removalfrom the vapour stream is by cyclone separation. Solids separationequipment (e.g. cyclones) may also be used inside the hydroprocessingreactor (above a dense bed phase) to prevent the entrainment of solidparticles above a certain particle size.

Char may also be removed in accordance with the process of thisinvention by filtration from the vapour stream, or by way of filteringfrom a wash step-ebullated bed. Back-pulsing may be employed in removingchar from filters, as long as the hydrogen used in the process of thisinvention sufficiently reduces the reactivity of the pyrolysis vapoursand renders the char produced free-flowing. Electrostatic precipitation,inertial separation, magnetic separation, or a combination of thesetechnologies may also be used to remove char and catalyst fines from thehot vapour stream before further hydrofinishing, cooling andcondensation of the liquid product.

In accordance with one embodiment of this invention, cyclone separationfollowed by hot gas filtration to remove fines not removed in thecyclones may be used to remove the char. In this case, because thehydrogen has stabilised the free radicals and saturated the olefins, thedust cake caught on the filters is more easily cleaned than char removedin the hot filtration of the aerosols produced in conventional fastpyrolysis. In accordance with another embodiment of this invention, thechar and catalyst fines are removed by bubbling first stage product gasthrough a re-circulating liquid. The re-circulated liquid used is thehigh boiling point portion of the finished oil from this process and isthus a fully saturated (hydrogenated), stabilised oil having a boilingpoint typically above 370° C. Char or catalyst fines from the firstreaction stage are captured in this liquid. A portion of the liquid maybe filtered to remove the fines and a portion may be re-circulated backto the first stage hydropyrolysis reactor. One advantage of using are-circulating liquid is that it provides a way to lower the temperatureof the char-laden process vapours from the first reaction stage to thetemperature desired for the second reaction stage hydroconversion stepwhile removing fine particulates of char and catalyst. Another advantageof employing liquid filtration is that the use of hot gas filtrationwith its attendant, well-documented problems of filter cleaning iscompletely avoided.

In accordance with one embodiment of this invention, cyclone separationfollowed by trapping the char and catalyst fines in a high-porositysolid adsorbent bed is used to remove the char and catalyst fines fromthe vapour stream. Examples of high-porosity solid adsorbents suitablefor trapping char and catalyst fines include CatTrap® materialsavailable from Crystaphase.

Inert graded bed materials may also be used to remove the char andcatalyst fines from the vapour stream.

In accordance with another embodiment of this invention, large-size NiMoor CoMo catalysts, deployed in an ebullated bed, are used for charremoval to provide further deoxygenation simultaneous with the removalof fine particulates. Particles of this catalyst should be large,preferably in the range of from 15 to 30 mm in size, thereby renderingthem easily separable from the fine char carried over from the firstreaction stage, which is typically less than 200 mesh (smaller than 70micrometers).

Any ash and catalyst fines present may also be removed in the charremoval step.

The remaining product stream is then cooled to a temperature 150 to 400°C. Preferably, the stream is cooled to a temperature in the range offrom 250 to 350° C.

Depending on the composition of the remaining product stream, suchcooling may lead to condensation of aqueous and/or organic materials.Optionally, at this stage, therefore, any non-organic liquid produced inthis cooling step may be removed, for example by using a 3-phasegas/liquid separator. Any condensed organic material may be provided tothe hydroconversion reactor with the rest of the vapour-phasedeoxygenated hydrocarbon product for further processing.

Optionally before, or after cooling, if any sulfur is present in theremaining product stream, said product stream may be subjected to sulfurremoval. In the embodiment wherein the hydropyrolysis catalystcomposition is provided to the hydropyrolysis reactor vessel in asulfided or sulfurised form, such a sulfur removal step will berequired. In other embodiments of the invention, the need for a sulfurremoval step will depend on the amount of sulfur present in thebiomass-containing or biomass-derived feedstock.

Organic sulfur may be removed in a separate reactor containing ahydrodesulfurisation (HDS) catalyst. Suitable HDS reactors and catalystsare known in the art and suitable catalysts include sulfided NiMo orsulfided CoMo on oxidic support. Examples of oxidic supports includealumina, silica, titania, silica-alumina. A preferred catalyst forhydrodesulfurisation of the feed is a sulfided CoMo supported on aluminasupport. The HDS reactor may be operated at temperatures that are lowerthan those in the hydropyrolysis reactor, to avoid formation ofaromatics in this reactor. Such sulfur removal may also result inpartial oxygen removal.

Further, a gas clean-up system may be used to remove sulfur (in the formof H₂S). This may be achieved, for example, by contacting the streamwith a sulfur guard bed. Suitable materials for such a sulfur guard bedinclude highly dispersed metals or metal oxides on an oxidic support ora metal oxide. Examples of metal oxides suitable as guard bed includezinc oxide and iron oxide. Examples of oxidic support include silica,alumina, and mixed silica-alumina. Suitable metals dispersed on oxidicsupport include nickel, iron, and copper. Suitable metal oxidesdispersed on oxidic support include iron oxide, zinc oxide and cupricoxide. Suitable loadings of active metal or metal oxide on the supportrange from 2 wt % to 70 wt % based on calcined, oxidic form of the guardbed material.

Hydroconversion Reactor

After removal of the char and cooling, the partially deoxygenatedhydrocarbon product together with the H₂, CO, CO₂, H₂O, and C₁-C₃ gasesfrom the hydropyrolysis step are contacted with one or more catalystcompositions in a hydroconversion reactor. Said one or more catalystcompositions comprise catalysts suitable for hydrodeoxygenation andaromatic saturation. This step is suitably carried out at a temperaturein the range of from 150° C. to 400° C. and a pressure in the range offrom 0.50 MPa to 7.50 MPa. The weight hourly space velocity (WHSV) forthis step is in the range of about 0.1 h¹ to about 2 h⁻¹.

The hydroconversion reactor may comprise one or more reactor vesselsand/or one or more reaction zones within a reactor vessel. Each reactorvessel and/or reaction zone may operate under different reactionconditions, e.g. temperature and pressure. Preferably, thehydroconversion reactor is a single reactor vessel.

The catalyst compositions used in this step are protected from Na, K,Ca, P, and other metals present in the biomass which may otherwisepoison the catalyst, since these metals are predominantly removed withthe char and ash products of the first hydropyrolysis stage, which areseparated from the partially deoxygenated hydropyrolysis product, priorto subjecting this product to hydroconversion. Further, the catalystcompositions used in this step are protected from sulfur either due tothe use of the non-sulfided catalyst in the hydropyrolysis step or dueto the use of the sulfur removal step, or both.

The one or more catalyst compositions suitable for hydrodeoxygenationand aromatic saturation preferably comprise a single catalystcomposition having activity for hydrodeoxygenation and aromaticsaturation. However, the use of two separate catalyst compositionseither in a mixed bed or in stacked beds within the hydroconversionreactor is envisaged within the scope of this invention.

In one embodiment of the invention, the catalyst composition present inthe hydroconversion reactor preferably comprise one or more activemetals selected from base metals comprising of cobalt, molybdenum,nickel and tungsten.

In this embodiment of the invention, the metals present in the catalystcomposition present in the hydroconversion reactor are supported,preferably on a metal oxide support. Metal oxides useful as supports forthe hydropyrolysis catalyst composition include alumina, silica,titania, ceria, zirconia, as well as binary oxides such assilica-alumina, silica-titania and ceria-zirconia. Preferred supportsinclude alumina, silica and titania. The most preferred support isalumina. The support may optionally contain recycled, regenerated andrevitalised fines of spent hydrotreating catalysts (e.g. fines of CoMoon oxidic supports, NiMo on oxidic supports and fines of hydrocrackingcatalysts containing NiW on a mixture of oxidic carriers and zeolites).Another class of materials suitable as support includes carbon-basedmaterials, including activated carbon, ordered mesoporous carbon anddisordered or worm-hole like mesoporous carbons.

Further, in this embodiment of the invention, the catalyst compositionmay be provided to the hydroconversion reactor in either an oxidic stateor in a pre-reduced state.

Therefore, after preparation by one of the above or another method, thecompositions thus-formed are suitably calcined in the presence of air oroxygen in order to obtain the oxidic state. By the term ‘oxidic state’as used herein is meant that 95% or more of the active metal atomspresent are present in an oxidation state greater than zero as oxides.For example, a supported oxidic cobalt catalyst has more than 95% of thecobalt present in the +2 or +3 oxidation state, as oxides, and asupported oxidic nickel catalyst has more than 95% of the nickel presentin the +2 oxidation state, as oxide.

Alternatively, after preparation by one of the above or another method,the compositions thus-formed are suitably subjected to a reduction stepin order to convert at least a portion of the active metals into theirfully reduced state. This can be carried out by subjecting the catalystto a reducing gas (for example, gas containing hydrogen) at elevatedtemperatures and elevated pressures. The temperatures of the reductionstep can vary from 120° C. to 450° C. and pressures can vary from 0.1megapascal to 10 megapascal.

It will be readily apparent that, although the catalyst compositionprovided in the hydroconversion reactor will initially comprise metal ormetals in their oxidic or reduced states, the chemical form of thecatalyst composition will undergo a change under the operatingenvironment of the process, resulting in a change in the chemical formof the active metals on the catalyst and of the support as well. Thischange will involve phenomena resulting from the interaction of thecatalyst with the reactant gas (hydrogen, carbon monoxide, carbondioxide), products (hydrocarbons) and by-products (water, carbonmonoxide, carbon dioxide, ammonia, traces of hydrogen sulfide, etc.)under the temperature and pressure conditions of the process.

It is postulated, without wishing to be bound by theory, that theinitial chemical composition will be transformed under the conditions ofthe process of the invention into a composition where a portion of theactive metals may be in reduced form (with an oxidation number of zero),and another portion of the active metals may be in a higher oxidationstate in oxidic form (with oxygen atoms available from the biomassfeedstock or from the catalyst itself). A small amount of the activemetals may also be present in sulfided form due to trace amounts ofsulfur present in the hydroconversion reactor.

In an alternative embodiment of the invention, the catalyst compositionpresent in the hydroconversion reactor preferably comprise one or moreactive metals selected from platinum group metals (ruthenium, rhodium,palladium, osmium, iridium, and platinum) and supported on an oxidesupport. Examples of oxide supports suitable for the catalystcomposition of this embodiment include alumina, silica, titania, ceria,zirconia, as well as binary oxides such as silica-alumina,silica-titania and ceria-zirconia. Another class of materials suitableas catalyst support includes carbon-based materials, including activatedcarbons, ordered mesoporous carbons and disordered or worm-hole likemesoporous carbons. Preferred supports include alumina, silica andsilica-alumina, and most preferred support is silica-alumina. Metalloadings on the support, expressed as weight percent of metal in itsreduced form on the catalyst, ranges from 0.05 wt % to 3 wt %.

For either embodiment of the invention, with respect to the catalystcompositions present in the hydroconversion reactor, total metalloadings on said catalyst compositions are preferably in the range offrom 0.05 wt % to 3 wt % for noble metals (e.g. ruthenium, platinum,palladium and iridium) and from 1 wt % to 75 wt % for base metals (e.g.cobalt, molybdenum, nickel, tungsten and iron) (weight percentages areexpressed as a weight percentage of total of all active metals on thecalcined catalyst in their reduced (metallic) form).

Also, in either embodiment, additional elements such as one or more ofphosphorous, boron and nickel may be incorporated into the catalystcomposition present in the hydroconversion reactor in order to improvethe dispersion of the active metal.

The catalyst composition used in the hydroconversion reactor in theprocess of the present invention may be prepared by any suitable methodknown in the art. Suitable methods include, but are not limited toco-precipitation of the active metals and the support from a solution;homogeneous deposition precipitation of the active metals on thesupport; pore volume impregnation of the support with a solution of theactive metals; sequential and multiple pore volume impregnations of thesupport by a solution of the active metals, with a drying or calcinationstep carried out between successive pore volume impregnations;co-mulling of the support with a solution or a powder containing theactive metals. Further, a combination of two or more of these methodsmay also be used.

The catalyst compositions present in the hydroconversion reactor arepreferably present as extrudate catalyst particles. Any suitableextrudate shape, e.g. cylinders, trilobes, tetralobes, may be used.

Catalyst particles sizes, for use in a commercial reactor in thehydroconversion step are preferably of a nominal diameter in the rangeof from 0.3 mm to 4.0 mm, more preferably in the range of from 0.6 mm to3.0 mm, and most preferably in the range of from 1 mm to 2.4 mm.Suitable lengths of the extrudate catalyst particles are in the range offrom 3 to 6 mm.

The hydroconversion reactor is preferably a fixed bed reactor operatingin either a down-flow or up-flow, preferably down-flow, mode ofoperation. Depending on the physical state of the feed to this reactor,it may operate under a trickle flow or a gas flow regime.

After the hydroconversion step, the vapour phase product of step d) maybe condensed to provide a liquid phase product comprising substantiallyfully deoxygenated C4+ hydrocarbon liquid and aqueous material. Theremaining vapour phase suitably comprises mainly H₂, CO, CO₂ and lighthydrocarbon gases (typically C₁ to C₃, but this stream may also containsome C₄₊ hydrocarbons) and may be separated.

This remaining vapour phase may optionally be sent to a gas clean-upsystem to remove H₂S, ammonia and trace amounts of organicsulfur-containing compounds, if present as by-products of the process.The stream containing CO, CO₂, H₂ and light hydrocarbons may then besent to a separation, reforming and water-gas shift section of theprocess, wherein hydrogen is produced from the light gases and may bere-used in the process. Preferably, this process provides enoughhydrogen for use in the entire process of the invention. Renewable CO₂is discharged as a by-product of the process.

The liquid phase product is then separated in order to remove theaqueous material, suitably by phase separation, and to provide thehydrocarbon product in the form of a deoxygenated hydrocarbon liquid.

The liquid deoxygenated hydrocarbon product herein preferably comprisesno more than 5 wt %, more preferably no more than 1 wt % of the oxygenpresent in the original biomass-containing and/or biomass-derivedfeedstock. The liquid deoxygenated hydrocarbon product contains lessthan 2 wt %, preferably less than 1 wt %, and most preferably less than0.1 wt % oxygen.

Suitably, the liquid deoxygenated hydrocarbon product is then subjectedto further separation and purification steps in order to providedesirable products.

In one embodiment of the invention, the liquid deoxygenated hydrocarbonproduct is subjected to distillation in order to separate the liquiddeoxygenated hydrocarbon product into C₄₊ fractions according to rangesof the boiling points of the liquid products contained therein.

The liquid deoxygenated hydrocarbon product comprises naphtha rangehydrocarbons, middle distillate range hydrocarbons and vacuum gasoil(VGO) range hydrocarbons, which can be separated by distillation. Forthe purpose of clarity, middle distillates here are defined ashydrocarbons or oxygenated hydrocarbons recovered by distillationbetween an atmospheric-equivalent initial boiling point (IBP) and afinal boiling point (FBP) measured according to standard ASTMdistillation methods. ASTM D86 initial boiling point of middledistillates may vary from 150° C. to 220° C. Final boiling point ofmiddle distillates, according to ASTM D86 distillation, may vary from350° C. to 380° C. Naphtha is defined as hydrocarbons or oxygenatedhydrocarbons having four or more carbon atoms and having anatmospheric-equivalent final boiling point that is greater than 90° C.but less than 200° C. A small amount of hydrocarbons produced in theprocess (typically less than 10 wt % of total C4+ hydrocarbons,preferably less than 3 wt % of total C4+ hydrocarbons and mostpreferably less than 1 wt % of total C4+ hydrocarbons) boil attemperatures higher than those for the middle distillates as definedabove, i.e. they are hydrocarbons with boiling range similar tovacuum-gas oil produced by distillation of petroleum.

Gasoline is an automotive fuel comprising predominantly of naphtha-rangehydrocarbons, used in spark-ignition internal combustion engines. In theUnited States, ASTM D4814 standard establishes the requirements ofgasoline for ground vehicles with spark-ignition internal combustionengines.

Diesel is an automotive fuel comprising predominantly ofmiddle-distillate range hydrocarbons, used in compression-ignitioninternal combustion engines. In the United States, ASTM D975 standardcovers the requirements of several grades of diesel fuel suitable forvarious types of diesel engines.

An advantage of the present invention is that under suitable operatingconditions, the liquid deoxygenated hydrocarbon product produced fromthe biomass-containing and/or biomass-derived feedstock, may besubstantially fully free from oxygen, sulfur and nitrogen and have lowcontent of aromatic compounds. Preferably, the oxygen content of thisproduct is less than 1.50 wt % and more preferably less than 0.50 wt %,and most preferably less than 0.10 wt %. The sulfur content ispreferably less than 100 ppmw, more preferably less than 10 ppmw, andmost preferably less than 5 ppmw. The nitrogen content is preferablyless than 1000 ppmw, more preferably to less than 100 ppmw and mostpreferably to less than 10 ppmw. The aromatics content is preferablyless than 10 wt %, more preferably less than 7 wt %, even morepreferably less than 5 wt %.

DETAILED DESCRIPTION OF THE DRAWINGS

FIG. 1 shows an embodiment of a prior art hydropyrolysis/hydroconversionprocess.

Feedstock 1 containing the lignocellulosic material is contacted with ahydrogen-containing gaseous stream 2 in hydropyrolysis reactor vessel 3.The product 4 of this reactor vessel is a mixed solid and vapour phaseproduct containing hydrogen, light gases (C₁-C₃ hydrocarbons, CO, CO₂,H₂S, ammonia, water vapour), vapours of C4+ hydrocarbons and oxygenatedhydrocarbons. Char, ash and catalyst fines are entrained with the vapourphase product. A solid separator 5 separates char, ash and catalystfines 6 from the vapour phase product stream 7. The vapour phase productstream 7 then enters the catalytic hydroconversion reactor 8. Thisreactor 8 is a fixed bed reactor. The product 9 of this reactor containslight gaseous hydrocarbons (methane, ethane, ethylene, propane, andpropylene), naphtha range hydrocarbons, middle-distillate rangehydrocarbons, hydrocarbons boiling above 370° C. (based on ASTM D86),hydrogen and by-products of the upgrading reaction such as H₂O, H₂S,NH₃, CO and CO₂. The vapours are condensed in one or more condensersfollowed by gas-liquid separators 10 downstream of the catalytichydroconversion reactor 8 and a liquid product 21 is recovered. Thenon-condensable gases 11 are sent to a gas clean-up system, comprising avapour phase hydrodesulfurisation reactor 12, an H₂S removal unit 13 toremove a H₂S stream 14 and an ammonia removal unit 15 to remove anammonia stream 16 as by-products of the process. The remaining streamcontaining light hydrocarbons 17 is sent to a separation, reforming andwater-gas shift section 18 of the process, where hydrogen 19 is producedfrom the light gases and renewable CO₂ is discharged as a by-product ofthe process 20. A fuel gas stream may be recovered as a by-product fromthis section as well.

The condensables 21 recovered from the condensation and gas-liquidseparation system 10 are sent to a liquid/liquid separator 23, where theaqueous product 22 is separated from the hydrocarbon liquid product 24.The hydrocarbon liquid product 24 is then sent for distillation 25 torecover gasoline product 26 and a middle-distillate product 27. Ifdesired, kerosene/jet fuel and diesel may be recovered as separatestreams from the distillation tower.

FIG. 2 exemplifies a prior art hydropyrolysis/hydroconversion processwith extra upgrading steps, such as described in WO 2015/114008. Theembodiment shown in FIG. 2 includes the same steps as the embodiment ofthe prior art shown in FIG. 1. However, an additional fixed-bedhydrogenation reactor 35 is used for upgrading the middle distillatefraction 28 recovered by the distillation of the hydrocarbon product 24of the hydroconversion reactor 8. A pump 30 is used to provide a stream31 comprising the middle distillate stream and a C6 stream rich inbenzene 29 from the distillation 25, to the reactor 35. A stream ofhydrogen 32 is compressed in a compressor 33 in order to provide ahydrogen stream 34 at a pressure that is similar to or higher than thepressure at which the hydropyrolysis and hydroconversion reactors (3, 8)operate. The stream 31 is pumped into the reactor 35 and processed overa hydrogenation (or hydrogenation & ring opening) catalyst system toproduce an upgraded product stream 36.

The upgraded product stream 36 is subjected to further distillation 37to provide an upgraded middle distillate product 38 and a C6 stream withreduced benzene 39. This C6 stream can be provided to a mixer 40 andmixed therein with the gasoline product 26 from distillation 25 in orderto provide an upgraded gasoline stream 41.

FIG. 3 exemplifies one non-limiting embodiment of the inventiondescribed herein. In this embodiment, the vapour phase product 7 fromthe solid separator 5 is subjected to a clean-up system, comprising avapour phase hydrodesulfurisation reactor 12, an H₂S removal unit 13 toremove a H₂S stream 14 and an ammonia removal unit 15 to remove anammonia stream 16 as by-products of the process. The resultant gaseousstream 42 is then cooled in cooler 43 and a gaseous cooled stream 44 isprovided to a fixed bed reactor 45. Fixed bed reactor 45 contains one ormore catalyst compositions suitable for hydrodeoxygenation and aromaticsaturation of the partially deoxygenated hydrocarbon product.

The vapour product stream 46 from reactor 45 is condensed in condenserand gas-liquid separator 47 downstream of the reactor 45 and a liquidproduct 48 is recovered.

Liquid product 48 is sent to a liquid/liquid separator 49, where theaqueous product 51 is separated from the hydrocarbon liquid product 50.The hydrocarbon liquid product 50 is then sent for distillation 51 torecover gasoline product 54 and a middle-distillate product 53. Ifdesired, kerosene/jet fuel and diesel may be recovered as separatestreams from the distillation tower.

The non-condensable gases 55 are sent to a separation, reforming andwater-gas shift section 56 of the process, where hydrogen 58 is producedfrom the light gases and renewable CO₂ is discharged as a by-product 57of the process.

A further non-limiting embodiment of the present invention is shown inFIG. 4. In this embodiment, cooling of stream 42 in cooler 43 results ina cooled stream 44 containing condensed materials. The cooled stream 44is then separated in three-phase separator 59 to separate a condensedaqueous stream 62, a condensed organics stream 61 and a gaseous stream60. Both the condensed organics stream 61 and gaseous stream 60 areprovided to the fixed bed reactor 45, which operates in this embodimentas a trickle-flow reactor.

FIGS. 5 to 10 show the results of the examples described herein.

EXAMPLES

The invention will now be illustrated by means of the followingExamples, which are not intended to limit the invention.

Example 1 (Comparative)

S-4211 catalyst (a cobalt/molybdenum catalyst commercially availablefrom CRI Catalyst Co) was crushed and sieved to a particle size range of300 μm to 500 μm. The catalyst was subjected to an ex-situ sulfidationprocedure to convert the cobalt and molybdenum metals to their sulfideforms. 210 g of this catalyst was used as the catalyst in the first,bubbling fluidised bed, hydropyrolysis reactor.

S-4212 catalyst (a nickel/molybdenum catalyst commercially availablefrom CRI Catalyst Co) was subjected to an in-situ sulfidation step toconvert the nickel and molybdenum metals to their sulphide forms. In thesecond, fixed bed reactor, 705 g of sulfided S-4212 catalyst was loadedin the form of extrudates of nominally 1.3 mm diameter and approximately3 mm to 6 mm length.

The solid feedstock used was sawdust of Pinus sylvestris ground andsieved to a particle size of less than 500 μm. The catalyst in thefirst, bubbling fluidised reactor was fluidised with a stream ofhydrogen pre-heated to a temperature of approximately 435° C. After thefirst stage catalyst had been fluidised, the biomass was introduced intothe reactor and processed in a continuous manner. The rate of processingof biomass was approximately 4.42 g/min on moisture and ash-free basisduring the experiment. This feed rate corresponds to a weight hourlyspace velocity of approximately 1.26 kg biomass fed per kg catalyst perhour (on a moisture and ash-free basis). Over the duration of biomassprocessing, the weighted average temperature of the fluidised bed ofcatalyst was 443.7° C. The biomass feedstock was converted to a mixtureof char, ash and vapours in the first, hydropyrolysis stage. Thefluidisation velocity was adjusted in such a way that the solid products(char, ash) and the vapour phase products were carried out of thereactor, while the catalyst remained in the reactor. Some catalyst wasattrited into fines, and the fines were carried out of the bed as well.

The solid product was separated from the vapour phase product in a hotfiltration set-up and the vapours were sent to the second stage fixedbed reactor. The average temperature of the second stage catalyst duringthe experiment was maintained at 410.5° C. The average weight hourlyspace velocity for the second stage was 0.38 kg biomass fed per kgcatalyst per hour (on a moisture and ash-free basis). Operating pressurefor both the first and the second stages was 2.25 MPa (gauge).

The vapour phase product of the second stage was cooled in stages to−41.8° C. and a two-layer liquid product containing a hydrocarbon layerfloating on an aqueous layer was recovered. The hydrocarbon liquid wasseparated from the aqueous liquid, and was analysed. The off-gas fromthe process was sent to an online gas chromatogram, and the compositionof the gas was analysed throughout the run. The mass balance and carbonbalance of the process was calculated from the mass and analysis of theliquid products and compositional information of the gas product, basedon which the yield profile was calculated.

It was found that the hydrocarbon liquid product had a very low oxygencontent (essentially below the detection limit of the instrument of 0.01wt %), and the aqueous product produced contained only 0.03 wt % carbon.Thus, complete hydrodeoxygenation of the biomass was achieved producingan oxygen-free hydrocarbon product, and a carbon-free aqueous phase. Thetotal acid number of the hydrocarbon product was found to be very low,less than 0.1 mg KOH/g.

The hydrocarbon and aqueous phases were subjected to further analysis.The detailed hydrocarbon analysis (DHA) of the hydrocarbon product (FIG.5) showed this product to be comprising predominantly of cyclic species.Among the cyclic species, naphthenes were found to dominate in the lowcarbon number range (carbon numbers of 7 and lower), while aromaticsdominated at higher carbon number range (carbon numbers of 8 and above).Paraffins and isoparaffins were present mainly in the low carbon numbermolecules (carbon numbers of 7 and lower). 6-carbon molecules were themost abundant molecules in the liquid product.

SIMDIS of the hydrocarbon product (FIG. 6) showed the product to beboiling predominantly in the gasoline and diesel range, with essentiallyno heavy hydrocarbons (boiling above 370° C.) produced. The yield of C4+hydrocarbons (hydrocarbons in the product having 4 or more carbon atoms)in this Example was found to be 26.6 wt % of the feedstock weight on amoisture and ash-free basis. Tables 1 to 8 show details of this example.

The aromatic content of the total liquid product (TLP) was also measuredusing IP-391 analytical method. This method showed the product tocontain about 53.6 wt % aromatics, with the contribution ofmonoaromatics at 41.4 wt % of the total liquid, that of diaromatics at7.4 wt % of the total liquid, and that of tri+ aromatics at 4.8 wt % ofthe total liquid.

Example 2 (Inventive)

S-4261 catalyst (a cobalt/molybdenum catalyst commercially availablefrom CRI Catalyst Co) was crushed and sieved to a particle size range of300 μm to 500 μm. 100 g of this catalyst was used as the catalyst in thefirst, bubbling fluidised bed, hydropyrolysis reactor. The weight ofcatalyst used in this inventive example is less than that in thecomparative example. This is done to achieve a higher weight hourlyspace velocity of biomass feedstock in the first stage. Since amount ofcatalyst or inorganic solid present in the reactor is expected toinfluence the residence time of biomass/char in the reactor,approximately similar inorganic solid loading were maintained in thefirst stage for Example 1 and Example 2 by adding to the hydropyrolysisreactor of Example 2 about 84.3 g of alumina powder not containing anyactive metals. The sieve fraction for alumina used was 355 μm to 600 μm.This alumina powder is expected to help in avoiding rapid entrainment ofbiochar from the reactor that would happen if only 100 g catalyst wereto be loaded in the reactor.

In the second, fixed bed reactor, a stacked bed of two differentcatalyst systems, comprising of S-4252 catalyst (a cobalt/molybdenumcatalyst available from CRI Catalyst Co) at the top and S-4213 catalyst(a Pt/Pd based hydrogenation catalyst commercially available from CRICatalyst Co) at the bottom was used. The weight ratio of the twocatalysts was 1:3, and the total mass of catalyst loaded was 520 g. Thecatalysts in the second, fixed bed, were loaded in the form ofextrudates of nominally 1.3 mm diameter and approximately 3 mm to 6 mmlength. Prior to introducing the biomass in the unit, the stacked bedcatalyst system in the second, fixed bed reactor, was reduced underflowing hydrogen at a pressure of approximately 2.25 MPa and atemperature of approximately 400° C.

The solid feedstock used was sawdust of Pinus sylvestris ground andsieved to a particle size of 250 μm to 500 μm. The catalyst in thefirst, bubbling fluidised reactor was fluidised with a stream ofhydrogen pre-heated to a temperature of approximately 435° C. After thefirst stage catalyst had been fluidised, the biomass was introduced intothe reactor and processed in a continuous manner. The rate of processingof biomass was approximately 5.33 g/min on moisture and ash-free basisduring the experiment. This feed rate corresponds to a weight hourlyspace velocity of approximately 3.20 kg biomass fed per kg catalyst perhour (on a moisture and ash-free basis). Over the duration of biomassprocessing, the weighted average temperature of the fluidised bed ofcatalyst was 433.7° C. The biomass feedstock was converted to a mixtureof char, ash and vapours in the first, hydropyrolysis stage. Thefluidisation velocity was adjusted in such a way that the solid products(char, ash) and the vapour phase products were carried out of thereactor, while the catalyst remained in the reactor. Some catalyst wasattrited into fines, and the fines were carried out of the bed as well.

The solid product was separated from the vapour phase product in a hotfiltration set-up and the vapours were sent to the second stage, a fixedbed reactor. Between the char filtration set-up and the second stage,the vapours were allowed to cool, and the average temperature of thesecond stage catalyst during the experiment was maintained at 265.4° C.The average weight hourly space velocity for the second stage was 0.62kg biomass fed per kg catalyst per hour (on a moisture and ash-freebasis). Operating pressure for both the first and the second stages was2.70 MPa (gauge).

The vapour phase product of the second stage was cooled in stages to−39.3° C. and a two-layer liquid product containing a hydrocarbon layerfloating on an aqueous layer was recovered. The hydrocarbon liquid wasseparated from the aqueous liquid, and was analysed. The off-gas fromthe process was sent to an online gas chromatogram, and the compositionof the gas was analysed throughout the run. The mass balance and carbonbalance of the process was calculated from the mass and analysis of theliquid products and compositional information of the gas product, basedon which the yield profile was calculated.

It was found that the hydrocarbon liquid product had a very low oxygencontent (about 0.01 wt %), and the aqueous product produced containedabout 0.28 wt % carbon. Thus, complete hydrodeoxygenation of the biomasswas achieved producing an oxygen-free hydrocarbon product, and a nearlycarbon-free aqueous phase. The total acid number of the hydrocarbonproduct was found to be very low, at 0.018 mg KOH/g.

The hydrocarbon and aqueous phases were subjected to further analysis.The detailed hydrocarbon analysis (DHA) of the hydrocarbon product (FIG.7) showed this product to be comprising predominantly of naphthenes,followed by paraffins (n- and iso-). 6-carbon molecules were the mostabundant molecules in the liquid product. SIMDIS of the hydrocarbonproduct (FIG. 8) showed the product to be boiling predominantly in thegasoline and diesel range, with essentially no heavy hydrocarbons(boiling above 370° C.) produced. The yield of C4+ hydrocarbons(hydrocarbons in the product having 4 or more carbon atoms) in thisExample was found to be 24.6 wt % of the feedstock weight on a moistureand ash-free basis. Tables 1 to 8 show details of this example.

The aromatic content of the total liquid product (TLP) was measuredusing IP-391 analytical method. This method showed the product to have avery low aromatic content. The monoaromatic, diaromatic and tri+aromaticcontent was each about 0.1 wt %, the detection limit of the method. Thetotal aromatic content in the total liquid product in this inventiveprocess scheme (<0.3 wt %) was thus significantly lower than that in thecomparative process scheme of Example 1 (53.6 wt %).

Example 3 (Inventive)

S-4261 catalyst (a cobalt/molybdenum catalyst commercially availablefrom CRI Catalyst Co) was crushed and sieved to a particle size range of300 μm to 500 μm. 135 g of this catalyst was used as the catalyst in thefirst, bubbling fluidised bed, hydropyrolysis reactor. The weight ofcatalyst used in this inventive example is less than that in thecomparative example. This is done to achieve a higher weight hourlyspace velocity of biomass feedstock in the first stage. Since amount ofcatalyst or inorganic solid present in the reactor is expected toinfluence the residence time of biomass/char in the reactor, wemaintained approximately similar inorganic solid loading in the firststage for Example 1 and Example 3 by adding to the hydropyrolysisreactor of Example 3 about 65 g of alumina powder not containing anyactive metals. The sieve fraction for alumina used was 355 μm to 600 μm.This alumina powder is expected to help in avoiding rapid entrainment ofbiochar from the reactor that would happen if only 135 g catalyst wereto be loaded in the reactor.

In the second, fixed bed reactor, a stacked bed of two differentcatalyst systems, comprising of S-4252 catalyst (a cobalt/molybdenumcatalyst available from CRI Catalyst Co) at the top and S-4213 catalyst(a Pt/Pd based hydrogenation catalyst available from CRI Catalyst Co) atthe bottom was used. The weight ratio of the two catalysts was 1:3, andthe total mass of catalyst loaded was 520 g. The catalysts in thesecond, fixed bed, were loaded in the form of extrudates of nominally1.3 mm diameter and approximately 3 mm to 6 mm length. Prior tointroducing the biomass in the unit, the stacked bed catalyst system inthe second, fixed bed reactor, was reduced under flowing hydrogen at apressure of approximately 2.25 MPa and a temperature of approximately400° C.

The solid feedstock used was sawdust of Pinus sylvestris ground andsieved to a particle size of 250 μm to 500 μm. The catalyst in thefirst, bubbling fluidised reactor was fluidised with a stream ofhydrogen pre-heated to a temperature of approximately 435° C. After thefirst stage catalyst had been fluidised, the biomass was introduced intothe reactor and processed in a continuous manner. The rate of processingof biomass was approximately 4.97 g/min on moisture and ash-free basisduring the experiment. This feed rate corresponds to a weight hourlyspace velocity of approximately 2.21 kg biomass fed per kg catalyst perhour (on a moisture and ash-free basis). Over the duration of biomassprocessing, the weighted average temperature of the fluidised bed ofcatalyst was 440.6° C. The biomass feedstock was converted to a mixtureof char, ash and vapours in the first, hydropyrolysis stage. Thefluidisation velocity was adjusted in such a way that the solid products(char, ash) and the vapour phase products were carried out of thereactor, while the catalyst remained in the reactor. Some catalyst wasattrited into fines, and the fines were carried out of the bed as well.

The solid product was separated from the vapour phase product in a hotfiltration set-up and the vapours were sent to the second stage, a fixedbed reactor. Between the char filtration set-up and the second stage,the vapours were allowed to cool, and the average temperature of thesecond stage catalyst during the experiment was maintained at 307.2° C.The average weight hourly space velocity for the second stage was 0.57kg biomass fed per kg catalyst per hour (on a moisture and ash-freebasis). Operating pressure for both the first and the second stages was2.70 MPa (gauge).

The vapour phase product of the second stage was cooled in stages to−42.3° C. and a two-layer liquid product containing a hydrocarbon layerfloating on an aqueous layer was recovered. The hydrocarbon liquid wasseparated from the aqueous liquid, and was analysed. The off-gas fromthe process was sent to an online gas chromatogram, and the compositionof the gas was analysed throughout the run. The mass balance and carbonbalance of the process was calculated from the mass and analysis of theliquid products and compositional information of the gas product, basedon which the yield profile was calculated.

It was found that the hydrocarbon liquid product had a very low oxygencontent (near the lower detection limit of the instrument at about 0.01wt %), and the aqueous product produced contained only about 0.15 wt %carbon. Thus, complete hydrodeoxygenation of the biomass was achievedproducing an oxygen-free hydrocarbon product, and a nearly carbon-freeaqueous phase. The total acid number of the hydrocarbon product wasfound to be very low, below 0.01 mg KOH/g.

The hydrocarbon and aqueous phases were subjected to further analysis.The detailed hydrocarbon analysis (DHA) of the hydrocarbon product (FIG.9) showed this product to be comprising predominantly of naphthenes,followed by paraffins (n- and iso-). 6-carbon molecules were the mostabundant molecules in the liquid product. SIMDIS of the hydrocarbonproduct (FIG. 10) showed the product to be boiling predominantly in thegasoline and diesel range, with essentially no heavy hydrocarbons(boiling above 370° C.) produced. The yield of C4+ hydrocarbons(hydrocarbons in the product having 4 or more carbon atoms) in thisExample was found to be 25.7 wt % of the feedstock weight on a moistureand ash-free basis. Tables 1 to 8 show details of this example.

The aromatic content of the total liquid product (TLP) was measuredusing IP-391 analytical method. This method showed the product to have avery low aromatic content. The monoaromatic content was about 1.4 wt %,while the diaromatic and tri+aromatic content was each below 0.1 wt %,the detection limit of the method. The total aromatic content in thetotal liquid product in this inventive process scheme (about 1.6 wt %)was thus significantly lower than that in the comparative process schemeof Example 1 (53.6 wt %).

TABLE 1 Example-1 Example-2 Example-3 Feedstock Pinus Pinus Pinussylvestris sylvestris sylvestris sawdust sawdust sawdust 1^(st) StageS-4211 S-4261/ S-4261 Catalyst Alumina 2^(nd) Stage S-4212 S-4252/S-4252/ Catalyst S-4213 S-4213 Stacked Stacked Bed Bed 1^(st) Stage 210100 135 Catalyst (S-4261) (S-4261) Weight, g 84.3 65 (Alumina) (Alumina)2^(nd) Stage 705 130 130 Catalyst (S-4252) (S-4252) Weight, g 390 390(S-4213) (S-4213) Weight of 784.1 1013.0 929.9 feedstock processed, g(MAF) Duration of 177.5 190.0 187 feedstock processing, min

TABLE 2 Feedstock Analysis Example-1 Example-2 Example-3 ¹Moisture, wt %6.51 4.96 3.46 Ash, wt % (dry 0.34 0.34 0.12 basis) ¹Moisture content isestimated from weight loss of the sample after drying at 103 ± 2° C.

TABLE 3 Feedstock Elemental Analysis (Moisture and ash-free (MAF) Basis)Example-1 Example-2 Example-3 Carbon, wt % 47.2 47.2 47.2 Hydrogen, wt %6.5 6.5 6.5 Oxygen, wt % 46.2 46.2 46.2 Sulfur, wt % 0.030 0.030 0.030Nitrogen, wt % 0.027 0.027 0.027 Feedstock H:C 1.64 1.64 1.64 AtomicRatio

TABLE 4 Operating Conditions Example-1 Example-2 Example-3 Average 443.7433.7 440.6 temperature in 1^(st) stage (° C.) Average 410.5 265.4 307.2temperature in 2^(st) stage (° C.) Average pressure 2.25 2.70 2.70(MPa(gauge))

TABLE 5 Yield Details All on MEF basis Example-1 Example-2 Example-3 C4+Hydrocarbon 26.6 24.6 25.7 Yield (wt %,) C1-C3 Hydrocarbon 15.1 15.217.3 Yield (wt %) CO Yield (wt %) 7.4 2.5 1.7 CO₂ Yield (wt %) 4.0 3.41.8 Char & Ash Yield 8.6 22.2 20.1 (wt %) Water Yield (wt %) 36.3 45.147.3 Hydrogen added 4.35 6.30 7.11 (wt %)

TABLE 6 condensed hydrocarbon liquid analysis Example-1 Example-2Example-3 Oxygen Content ⁴BDL ⁴BDL ⁴BDL (wt %) Carbon Content 88.7686.01 85.92 (wt %) Hydrogen Content 11.43 14.19 14.13 (wt %) Density(g/mL, at 0.8365 0.7955 0.7923 15° C.) Gasoline² in C4+ 69 72 74Hydrocarbon (%) Diesel³ in C4+ 31 28 26 Hydrocarbon (%) Total AcidNumber <0.01 0.018 <0.01 (TAN) H/C Atomic Ratio 1.53 1.97 1.96 ²Gasolineis defined here as containing hydrocarbons having between 4 and 10carbon atoms. ³Diesel is defined here as containing hydrocarbons with 11or more carbon atoms. ⁴BDL = below detection limits (0.01 wt % foroxygen measurement)

TABLE 7 C1-C3 gas composition* Example-1 Example-2 Example-3 Methane wt% 25.5 32.7 38.2 Ethane wt % 44.1 39.0 36.4 Propane wt % 30.4 28.3 25.4*normalised to 100%

TABLE 8 Water Analysis Example-1 Example-2 Example-3 pH 9.2 8.8 9.4Density (g/mL, at 1.0006 0.9971 0.9990 15° C.) Sulfur Content 264 3.83.9 (ppmw) Nitrogen Content 1132 171.8 654.1 (ppmw) Carbon Content 0.030.28 0.15 (wt %)

1. A process for producing liquid hydrocarbon products from at least oneof a biomass-containing feedstock and a biomass-derived feedstock, saidprocess comprising the steps of: a) contacting the biomass-containingfeedstock and/or biomass-derived feedstock with a hydropyrolysiscatalyst composition and molecular hydrogen in a hydropyrolysis reactorvessel at a temperature in the range of from 350 to 600° C., a pressurein the range of from 0.50 to 7.50 MPa and a WHSV in the range of greaterthan 2.0 kg (biomass)/hour/kg (catalyst), to produce a product streamcomprising a partially deoxygenated hydrocarbon product, H₂O, H₂, CO₂,CO, C₁-C₃ gases, char and catalyst fines; b) removing all or a portionof said char and catalyst fines from said product stream; c) cooling theremaining product stream to a temperature in the range of from 150 to400° C.; and d) hydroconverting all or a portion of said partiallydeoxygenated hydrocarbon product in a hydroconversion reactor in thepresence of one or more catalyst compositions suitable forhydrodeoxygenation and aromatic saturation of the partially deoxygenatedhydrocarbon product in the presence of the H₂O, CO₂, CO, H₂, and C₁-C₃gas generated in step a), to produce a vapour phase product comprising aC4+ hydrocarbon product, H₂O, CO, CO₂, and C₁-C₃ gases.
 2. The processas claimed in claim 1, wherein the hydropyrolysis catalyst compositioncomprises one or more active metals selected from cobalt, molybdenum,nickel, tungsten, ruthenium, platinum, palladium, iridium and iron,supported on a metal oxide support.
 3. The process as claimed in claim1, wherein the WHSV in the hydropyrolysis reactor vessel is no more than6 h⁻¹.
 4. The process as claimed in claim 1, wherein in step c) theremaining product stream is cooled to a temperature in the range of from250 to 350° C.
 5. A The process as claimed in claim 1, wherein before orafter cooling the product stream is subjected to sulfur removal.
 6. AThe process as claimed in claim 1, wherein the catalyst compositionpresent in the hydroconversion reactor comprises one or more activemetals selected from cobalt, molybdenum, nickel and tungsten supportedon a metal oxide support.
 7. The process as claimed in claim 1, whereinthe catalyst composition present in the hydroconversion reactorcomprises one or more active metals selected from ruthenium, rhodium,palladium, osmium, iridium, and platinum, supported on an oxide support.8. The process as claimed in claim 1, wherein the hydroconversionreactor is a fixed bed reactor.
 9. The process as claimed in claim 1,wherein after step d), the vapour phase product is condensed to providea liquid phase product comprising substantially fully deoxygenated C4+hydrocarbon liquid and aqueous material, which are then separated. 10.The process according to claim 9, wherein the substantially fullydeoxygenated C4+ hydrocarbon liquid comprises no more than 1 wt % of theoxygen present in the original biomass-containing and/or biomass-derivedfeedstock.
 11. The process according to claim 9, wherein thesubstantially fully deoxygenated C4+ hydrocarbon liquid is thensubjected to distillation.